Lubricating stabilizers for chlorine-containing polymers

ABSTRACT

Lubricating heat and light stabilizer compositions for chlorinecontaining polymers comprising a mixture of an organotin carboxylate and a metal salt of a monoalkyl ester of an unsaturated dicarboxylic acid, and plastic compositions prepared therefrom.

United States Patent Gloskey :.260/45.75

Lozanou 1 Feb. 22, 1972 [54] LUBRICATING STABILIZERS FOR 2,838,5546/1958 Gloskey ..260/45.75

CHLORINE-CONTAINING POLYMERS 2,938,013 5/ 60 3,296,289 l/1967 Gloskey..260/45.75 1 Invenwfl Merrill 14mm", East Lyme, Conn- 3,379,679 4/1968Besso ..260/45.75 A ig Chas a & Co. c. New Yor NIY' Pemeck [22] Filed:Dec. 11, 1969 Primary Examiner-Donald E. Czaja Assistant Examiner-V. P.Hoke [21] Appl' 884377 Attorney-Connolly and Hutz 52 Us. Cl ..260/23 XA,252/406, 252/407, 260/31.2 R, 260/3l.8 M, 260/31.8 R, 260/45.75 K, 7 r VV 260/45.s5, 260/899 1571 7 ABSTRACT [51] Int. Cl. ..C08f 45/62Lubricating heat and light Stabilizer compositions for Fleld of SearchK, X, M, chlorine containing polymers comprising a mixture of an or260/31.8 U, 31. M, 407 ganotin carboxylate and a metal salt of amonoalkyl ester of an unsaturated dicarboxylic acid, and plasticcompositions [56] References Cited prepared therefrom.

UNITED STATES PATENTS 5 Claims, No Drawings 2,307,092 1/1943 YngveLUBRICATING STABILIZERS FOR CHLORINE- CONTAINING POLYMERS BACKGROUND OFTHE INVENTION 7 color changes in the resin, which changes in color fromcolorless, to yellow, to red, to brown, and finally to black. Evenfinished articles will exhibit these color changes when maintained athigh temperatures or exposure to light for prolonged periods of time.

Degradation of the resin during processing also causes it to becomeinsoluble and infusible, thus making it difficult to prepare fabricatedarticles, or otherwise resulting in finished articles of inferiorquality. Furthermore, because of the undesirable characteristics ofresins which have undergone degradation, it becomes difficult toreutilize the waste scraps of resin obtained during the fabrication ofproducts. Degradation in the finished articles causes them to becomebrittle and suffer loss of strength. These degradation problems havebeen obviated in part by the addition of heat and light stabilizers tothe chlorine-containing polymers during processing. Among the heatstabilizers employed are the organotins, various lead compounds, andcadmium and zinc soaps. In particular, the metallic stearates, such ascadmium stearate, have been found to be good heat and light stabilizers.Nevertheless, the organotin compounds are the most efficient stabilizersfor chlorine-containing polymers. Unfortunately, their high costprecludes wider acceptance, and as a result their use is restricted tospecialized applications.

Another problem that arises during the processing of chlorine-containingpolymers, especially with polyvinyl chloride, is that of the lubricityof the fused blend. There is always a tendency during processing for theresin to plate out on the mill or calender rolls and stick to the heatedmetal parts. Consequently, it is customary to incorporate a lubricantwith the resin. The lubricant chosen, however, must establish theappropriate compatibility with the resin. If the lubricant is toocompatible it will tend to plasticize the polymer, and if tooincompatible it will tend to form a surface film or bloom on thefinished plastic article. It has also been found that some lubricantsare excellent heat and light stabilizers as well. These materials aredesignated lubricating stabilizers. The metallic stearates, such as zincstearate, have found wide application as lubricating stabilizers. On theother hand, some stabilizers such as the organotin maleates presentsticking problems during processing. In the latter situation appropriatelubricants or lubricating stabilizers must be added to the resin blendbefore processing.

It has now been found that various metal salts of certain monoalkylesters of unsaturated dicarboxylic acids are excellent lubricatingstabilizers for chlorine-containing polymers and when used with theorganotin stabilizers, in particular the organotin maleates, provideexcellent lubricity and heat and light stability. Plastic articlesprepared with these compounds exhibit heat stability and particularlylight stability, far superior to that shown by articles not containingthese compounds. In addition, the use of the metal salts of thesemonoalkyl unsaturated esters in conjunction with the organotins enablesone to use a lower level of the more expensive organotin with thechlorine-containing polymers and still obtain a high degree of heat andlight stability.

SUMMARY OF THE INVENTION This invention is concerned with novel plasticcompositions comprising chlorine-containing polymers, organotincarboxylates, and metal salts of monoalkyl esters of unsaturateddicarboxylic acids wherein the metal cation is either sodium, calcium,magnesium, or aluminum; the monoalkyl radical contains from eight to 18carbon atoms; and the unsaturated dicarboxylic acid is either maleicacid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, orglutaconic acid.

This invention is also concerned with novel lubricating heat and lightstabilizer compositions for chlorine-containing polymers which compriseorganotin carboxylates and metal salts of monoalkyl esters ofunsaturated dicarboxylic acids wherein the metal cation is eithersodium, calcium, magnesium, or aluminum; the monoalkyl radical containsfrom eight to 18 carbon atoms; and the unsaturated dicarboxylic acid iseither maleic acid, fumaric acid, itaconic acid, citraconic acid,mesaconic acid, or glutaconic acid.

DETAILED DESCRIPTION OF THE INVENTION The novel heat and lightstabilized plastic compositions of this invention comprise achlorine-containing polymer, an organotin carboxylate, and a sodium,calcium, magnesium, or

aluminum salt of the monoalkyl ester of the following unsaturateddicarboxylic acids: maleic acid, fumaric acid, itaconic acid, citraconicacid, mesaconic acid, and glutaconic acid.

The monoalkyl radical of the ester group can be branched or straightchain and contain from eight to 18 carbon atoms. Any chlorine-containingpolymer derived from an ethylenically unsaturated monomer can be used inpracticing the present invention. Typical examples include: poly(vinylchloride), vinyl chloride-vinyl acetate copolymers, vinylchloride-propylene copolymers, vinyl chloride-alkyl vinyl ethercopolymers, poly(vinyl chloride)-chlorinated polyethylene mixtures,mixtures of poly(vinyl chloride) and terpolymers ofacrylonitrile/butadiene/styrene, mixtures of poly(vinyl chloride) andterpolymers of methyl methacrylate/butadiene/styrene, mixtures ofpoly(vinyl chloride) and acrylic modifiers or ethylene-propylene rubber.

The lubricating heat and light stabilizer compositions are incorporatedwith the above polymers to give the desired plastic compositions. Thestabilizer compositions comprise an organotin carboxylate and thepreviously mentioned metal salts of the monoalkyl half-esters.

The use of organotin carboxylates containing up to 12 carbon atoms inthe carboxylate moiety is preferred in the present invention. Typicalrepresentatives include the following well-known compounds: dibutyl tinmaleate, di-n-octyl tin maleate, dibutyl tin bis(monocyclohexylmaleate), di-n-octyl tin bis(monocyclohexyl maleate), dibutyl tinbis(monomethyl maleate), di'n-octyl tin bis(monomethyl maleate), dibutyltin bis(mono-Z-methylhexyl maleate), di-n-octyl tin bis(monom octylmaleate), dibutyl tin dilaurate, and din'octyl tin dilaurate.

The organotin carboxylates have been described in the literature and arecommercially available. They can, however, be readily prepared bytechniques familiar to those skilled in the an. See, for example, Smith,Organotin Stabilizers, Tin Research Institute, Middlesex, England, 1959,pp. 56.

As mentioned above, it has now been found that superior lubricatingstabilizer compositions can be prepared by using these organotincarboxylates in conjunction with the calcium, sodium, aluminum andmagnesium salts of the aforementioned monoalkyl half-esters. Theselatter compounds are readily prepared by conventional syntheticprocedures well known to those skilled in the art. For example, themonoalkyl ester can be first prepared from the dicarboxylic acid and theappropriate alcohol by standard esterification reactions, and thenreacted with a metallic salt or base containing the desired metalliccation. The preferred salts in this series are the magnesium andaluminum monoalkyl maleates and fumarates, and in particular magnesiumand aluminum stearyl maleate.

Although the herein-described metal salts of the half-esters areeffective as lubricating stabilizers when used alone, the presentinvention contemplates their use in conjunction with the organotincarboxylates described above to give the novel stabilizing compositionsof the present invention.

The organotin carboxylates are well-known heat and light stabilizers forchlorine-containing polymers. Some of them, such as the dialkyl tindilaurates, are lubricating stabilizers as well. Nevertheless, many ofthe compounds in this series, in particular the dialkyl tin maleates, donot possess the requisite lubricity and must be used in conjunction withsuitable lubricating agents. It has now been found that when the metalsalts of the monoalkyl esters of the herein described unsaturated acidsare used in conjunction with these dialkyl tin carboxylates withchlorine-containing polymers there is an enhancement in the heat andlight stability of the resulting resin blend and the plastic articlesmanufactured therefrom. In addition, the metal salts of the monoalkylhalf-esters provide the lubricity needed for the processing of thechlorine-containing polymers into finished articles. Thus, the metalsalts are especially effective when used with the dialkyl tin maleates,providing not only increased light and heat stability, but the essentiallubricity as well. Accordingly, when used together, the organotincarboxylates and the metal salts of the monoalkyl esters of the hereindescribed unsaturated dicarboxylic acids provide lubricating heat andlight stabilizing compositions having superior characteristics.

Generally, 0.5 to 3.0 parts by weight of the organotin carboxylate and0.30 to 1.50 parts of the metal salts of the halfesters can be used per100 parts of the chlorine-containing polymers. An especially preferredformulation comprises l.0-2.0 parts of organotin carboxylate, 0.8-1.2parts of metal salt of the half-ester, and 100 parts of resin.

Other additives can be added to the polymer blend as required. Thus, forcertain purposes antioxidants would be added to protect againstoxidative degradation. Plasticizers can also be used without affectingthe properties of the stabilizing systems. It has been found that thecoaddition of an organotin mercaptide or organotin mercaptoester withthe lubricating stabilizer compositions of the present invention resultsin a further improvement in light stability and in particular heatstability. Among the organotin mercaptides that have been foundeffective are dibutyl tin bis (laurylmercaptide) and dibutyl tin bis(hexadecylmercaptide). Typical representatives of the organotinmercaptoesters include dibutyland di-n-octyl tin bis (Z-ethylhexylthioglycollate), and dibutyland di-n-octyl tin B-mercaptopropionate.

The carboxylates and the metal salts of the half-esters are usuallyfirst blended together before mixing them with the chlorine-containingpolymers, particularly where the stabilizer compositions are to bestored or transported before using. This aspect of the invention is notcritical, however, and if desired each component can be separately addedto the polymer and the blended mixture charged to a two roll mill heatedat about 350400 F.

The heat and light stability of the resultant flexible sheets are thendetermined. Standard accelerated test procedures such as the AtlasFadeometer Test, using UV light or the Xenotest UNIT, using a Xenonlight source, can be used. After exposure the samples are periodicallyexamined to determine the degree of discoloration which has occurred.The amount of discoloration of the samples is an indication of theextent of degradation that has taken place. Static and dynamic heatstability tests are then carried out. The static heat stability testsare conducted by placing a series of samples of the plastic sheets in acirculating air oven at about 360 F. for 3 hours and removing specimensat minute intervals and determining the degree of discoloration. Thedynamic heat stability tests are conducted by continuously millingvarious formulations containing the stabilizing compositions at 350 F.Specimens are taken at 2 minute intervals and examined fordiscoloration.

Extended outdoor experiments were also conducted in Arizona and Floridato determine the light stability and rate of deterioration of physicalproperties of plastic compositions containing the herein describedstabilizers over long periods of time. Comparison tests were run usingcommercial stabi1- izers as well. The results clearly show that thestabilizer compositions of the instant invention provide a remarkabledegree of heat and light stability to the finished chlorine-containingpolymer articles as well as providing excellent lubricity and heat andlight stabilityto the chlorine-containing polymers during processing.The finished plastic articles employing the instant stabilizercompositions are found to possess outstanding clarity, color, andsurface gloss.

The following examples are provided to illustrate further the scope ofthe present invention, but should not be construed as limitationsthereof.

EXAMPLE I Light Stability Studies A. Outdoor Exposure The formulationsbelow were milled on a two roll plastic mill with roll friction ratio of121.4 (Model 3-V-500 Research Mill, Farrel Corporation, Ansonia,Connecticut). Mill temperature was set at 350 F., and milling time was 6minutes. The milled sheets were press polished between ferrotype platesat 375 F., 1,000 psi. for 3 minutes. Thickness of the finished samplesvaried from 30 to 40 mils.

Ingredients, weight per hundred parts Sample No. of resin (phr) l 2 3 45 6 7 8 Medium molecular weight polyvinyl chloride (PVC) homopolymerresin (average molecular weight ca. 140,000, K=68) obtained from B. F.Goodrich Chemical Co., Cleveland, Ohio.

Dlbutyl tin bis (methyl malcate) heat and light stabilizer, supplied byChas. Pfizer & Co., Inc., New York, New York.

Benzotriazole-type ultraviolet light absorber supplied by Gcigy ChemicalCo., Ardsley, New York.

Low molecular weight polyethylene lubricant supplied by Allied ChemicalCo., New York, New York.

Panels having the above composition were mounted against well-agedpinewood backing and set outdoors facing 45 South in Phoenix, Arizona.

The results obtained are listed below.

Amount of Exposure Required for Sample to Undergo Sample Langleys UVSHYellow Discoloration 1 [34,766 l39l 10 months 2 134,766 I391 10 months 3[34,766 1391 10 months 4 119,020 1244 9 months 5 149,l40 1510 ll months6 149,l40 1510 ll months 12 months 15 months Langley is onegram-calorielcm.

UVSH (ultraviolet sun hour) is defined as any 60 minute period duringwhich the sun intensity exceeds0.823 gram-calories/cm min. (0.823Langley/min.)

Ingredients Sample No.

Weight per hundred parts of resin (phr) 9 10 11 12 Geon 103EPF7 resin100 100 100 100 Stanguard 156 20 20 1.8 Dibutyltin his (cyclohexylmaleate) 2.0

Stearic acid 0.5

Hoechst wax GL-3 0.6 0.6

Hoechst wax OP 0.4 0.4

Magnesium monostearyl maleate 10 PVC lubricants supplied by AmericanHoechst Corp., Mountainside, New Jersey.

Sample No. 9 10 11 12 Hours olexposure in Xenotest 150 needed to causeyellow discoloration 1250 600 600 2000 Accelerated light stability testswere also conducted with an Atlas Fadeometer (Atlas Electric DevicesCo., Chicago, Illinois).

The samples below were prepared in the manner indicated above.

Ingredients Sample No.

Weight per hundred parts of resin (phr) 13 14 15 Exon 9269 100 100 100Dibutyltin maleate T-290 1.00 1.00 1.00 Hoechst wax OP 0.50

Hoechst wax GL 0.50

A/C P1362) 0.10 Magnesium monostearyl maleate 1.00 1.00

Mcdium'low molecular weight (ca. 120.000. K=64) homopolymcr PVC resinobtained from Firestone PlasticsCo, Pottstown. Pa.

The fadeometer results are given below:

F ADEOMETER RESULTS Time Sample Sample Sample No. 13 No. 14 No. 15

Initial slightly clear/colorless slightly cloudy] Color opaque! slightlyyellow slightly yellow 100 hours slightly clear/colorless slightly redtint brown 200 hours darker clear/colorless slightly red tint brown 300hours dark clear/colorless very slightly brown brown 400 hours blackishtint of red slightly brown brown 500 hours grayish tint or red slightlybrown black 600 hours grayish tint of red slightly brown black 700 hoursgrayish tint of red slightly brown black 800 hours grayish reddish veryslightly brcwn/ very black small brown small black specks specks 900hours black more brown slightly brown! specks additional black specks1000 hours black light brown/ slightly brown! black specks additionalblack specks 1 hours black light brown/ slightly brown] black specksadditional black specks 1200 hours black light brown/ blackish brown/black specks small black specks From the above results, it is seen thatthe magnesium monostearyl maleate improves the formulation and vastlyextends the exposure time before discoloration occurs. it is furtherapparent that magnesium monostearyl maleate permits the use of lowerconcentrations of the more expensive organotin stabilizer whileimproving performance, thus reducing the overall cost of theformulation.

It has previously been shown that lead salts, such as basic leadsilicate, with monoalkyl fumarates or monoalkyl maleates are good heatstabilizers. Results of accelerated and outdoor exposures describedabove have demonstrated that lead derivatives are poor lightstabilizers, however, and actually detract from the light stabilizingeffectiveness of the organotin maleate esters.

It has also been shown that certain inorganic magnesium salts improvethe light stability of poly(vinyl chloride). Accordingly, effectivenessof these systems was determined with the formulations listed in thetables below and compared to the system containing magnesium monostearylmaleate:

in Xenotest needed to cause yellow discoloration The samples containingtrimagnesium phosphate (No. 17) and basic magnesium carbonate (No. 18)were yellower in color, had poorer clarity than the control (No. 16),and showed considerably more flexural stress whitening. The samplescontaining magnesium stearyl maleate (Nos. 19 8L 20), on the other hand.showed marked improvement in stability and gave much better initialcolor than the control, water-white by comparison, with as good. if notbetter, clarity and less stress whitening.

The accelerated tests above show the inorganic salts to be inferior inenhancing light stability. After 400 hours of Xenotest exposure,Formulations No. 17 and 18 began to discolor and develop haze whereasafter 800 hours No. 19 and 2O appeared colorless and unchanged inclarity. (The control started to discolor after 200 hours.) Based onprevious correlations between Xenotest exposure and outdoor weathering,these results indicate that more than a fourfold improvement longer termstability. As shown above, a reduction in the level of the moreexpensive organotin stabilizer is possible without loss in stabilizingactivity as compared to control.

B. Dynamic Heat Stability can be obtained by the use of the magnesiumsalts of the The dynamic Stability Ofthe 3 Samples below wasdeterpresent invention. mined by milling the formulations continuouslyat 350 F., with a back roll speed of 40 feet per minute until completeEXAMPLE H degradation had occurred. The specimen chips were sampled HeatStability Studies 10 at 2 minute intervals to show the colordevelopment. Ingredient, Sample No. A. Static Heat Stability Weight perhundred The formulations below were milled for 6 minutes at a roll Pam(PM) 31 temperature of 350 F. and sheeted at 40 mils. Samples from thesheets were subjected to heat in a circulating air oven at O3EPF7 100I00 I00 l'eSlll 356 for 3 hours (180 minutes) with specimens removed atsmmouard 2'0 2,0 m l5 minute intervals to show the heat history.Comparisons for A/C PE629 0.2 initial color were made on the milledsheets and noted as 0 (0 Magnesium Mono minutes) time Stearyl Maleate0.75 1.0

Ingredients, Sample number weight per hundred parts of resin (phr.) 2122 23 24 25 26 27 28 29 30 Geon 103 EPF 7 resin- 100 100 100 100 100 100100 100 100 100 Stan-Guard 156 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2. 0 2.0 1.8A/C PE 629 0.2 Calcium stearate 1. 0 Aluminum stearate 1. 0 Magnesiumstearate 1. 0 Calcium monosteary maleate 1.0 Aluminum monostearyl male-1 0 8. 4 V a v M nesium monostear lmale- 2 Y 1.0 1 0 Aluminummonostearyl fumarate 1.0 Magnesium monostearyl furnarate 1.0

U i I v -u A Vfwnm Sam 6 Sample: Physical appearance P 21 Excellentclarity. Milling e eq d t 22 Translucent. 1:7 :5 I a. lg c0 or g2 Falrgg b. Intense Color 60' 66' 60' r c. Degradation (term) 74' 86' 74' 3gExc clarity C010! a! B black dark tan dark tan e 27 The data obtainedabove with the d namic millin 28 Good clarity. y g

- rocedure shows that magnesium monostear l maleate ro- 29 Fair clarity.P 30 E ll t l it vlde at least as good if not better early stability asthe control The static heat stability results are given below.

STATIC HEAT STABILITY AT 356 F.

l 0 Colorless; 1 =Very slightly yellow; 2= Slightly-moderately yellow;3= Yellow; 4= Deep yellow; 5= Black. A rm The above results show thatthe metal derivatives of the half-esters are highly efiective inenhancing heat stability and are much better than the correspondingsalts of the fatty acids. They provide better initial color, less colordevelopment, and

with less color development and significantly longer term.

Dynamic termal stability (DTS) studies were determined with theformulations below in a Brabender Plasticorder (C. W. BrabenderInstruments, Inc., South Hackensack, New Jersey).

The formulations were charged to an intensive mixer, Roller No. 6measuring head attachment to the Brabender Plasticorder. This instrumentrecords the work required for mixing in terms of metergrams of torque,and also records the temperature during mixing. The time to degradationis determined from the torque curve and is a measure of the DTS ordynamic thermal stability of the formulation. The data was obtainedusing the following conditions:

Jacket temperature 1 25 C.

Shear rate r.p.m.

Charge-57 grams The formulations and results are given below.

Ingredient, weight per hundred parts of resin (phn) Sample Number Geon103 EPF 7 resin Acryloid K-N 1 AK] PE 629 Sodium monostearly maleaCalcium monostearyl maleatm. Aluminum monostearyl maleat Fusion torque,metergrams 7, 000 6, 900 6, 750

Steady state torque, metergrams. 3, 750 3, 750 3, 700 3, 700 3, 700 3,750 3, 725 3, 775 3, 800 Stock temperature, C 187 187 184 185 185 186185 185 DTS, minutes 8. 3 21. 5 16. 3 13. 0 15.5 20. 7 21.5 17. 5 20.0

The above results show that corresponding salts of the fumarate ester(Sample Nos. 39-42) exhibit outstanding term stability. The use of thesecompounds would allow greater reprocessing of scrap resin.

Comparative heat stability studies were determined with Samples l3, l4and 15 of Example I.

The Mill Testing was run at 350 F., 375 F., and 400 F., on two roll millat 30 f.p.m. with continuous rolling bank. The results are given below:

Temperature 350 F.

The magnesium monostearyl maleate increased heat stability andincorporated a fair degree of lubricity. Resin with dibutyltin maleateT-290 and no lubricant stuck immediately to the mill.

EXAMPLE 111 Effects of Outdoor Exposure on Physical CharacteristicsClear, rigid PVC panels, 5 inches X 3 inches X 0.045 inch, were preparedfrom the formulations below, and were set outdoors in Sarasota, Floridafor 2 years. The panels were mounted against wood backing facing 45South. The total radiation over this period was 322,057 langleys at4,102 ultraviolet sun hours. The total rainfall during this period was80 inches.

b. vinyl chloride/vinyl acetate copolymer (VYNW, Union Carbide PlasticsCo., New York, New York) c. vinyl chloride/propylene copolymer (Airco401, Airco Chemicals and Plastics, New York, New York) d. vinylether/vinyl chloride copolymer (Plaskon PVC CG014, Allied ChemicalCorp., New York, New York) e. ethylene-propylene rubber f. chlorinatedpolyethylene (Allied Chemical Corp., New

York, New York) g. acrylonitrile/butadiene/styrene terpolymer (Blendex401,

Marbon Chemical, Div. of Borg-Wamer Corp., Washington W.V.)

h. methyl methacrylate/butadiene/styrene terpolymer (KM 607, Rohm andHaas Co., Philadelphia, Pennsylvania) i. internally plasticizedpo|y(vinyl chloride) copolymers (Vinnol H 315/65, Wacker Chemie GMBH.Munich. West Germany) j. vinyl ester/ethylene modified poly(vinylchloride) (Vinnol WI 350, Wacker Chemie GMBl-I) EXAMPLE V When thedibutyltin bis( methyl maleate) (Stan-Guard 156) in Samples 1, 3-12, and21-42 and the dibutyl tin maleate (Advastab T-290) in Samples 13-20 inthe above examples, are replaced with an equivalent amount of theorganotin carboxylates listed below, substantially the same results areobtained:

a. dibutyl tin dilaurate b. di-n-octyl tin dilaurate c. di-n-octyl tinmaleate d. dibutyl tin bis(monocyclohexyl maleate) e. di-n-octyl tinbis( monocyclohexyl maleate) f. di-n-octyl tin bis(monomethyl maleate)g. dibutyl tin bis(mono-Z-ethylhexyl maleate) h. dibutyl tin monolauratemono(2-ethylhexyl maleate) i. dibutyl tin bis(monostearyl maleate) j.di-n-octyl tin bis(mono-n-octyl maleate) PERCENT RETENTION OF PHYSICALPROPERTIES Ulti- Yield mate Tensile Yield Elon- Tensile elon modulus,strength, gation, strength, gation,

Sample Ingredients 1 percent percent percent percent percent Number: v

fig fl g' 1 85 105 112 104 30 43M Sample 43zu1d Ilnskon 103 l impactmodifier. 94 106 98 101 Stan-Guard 156 2.0 phr 44 .5... lllaglgnesiunistein'yl maleate 0.75 94 105 116 104 p n'. 44M Sample 44 and Plaskon 10396 107 112 100 52 impact modifier. Stan Guard 156, 2.0 phr 45 Alufininumsteaiyl maleate 0.75 95 109 117 110 40 p r. 45M Sample 45 and Plaskon103 07 107 106 100 47 impact modifier.

1 Based on 100 parts Geou 103EPF7 resin (phr.). 2 Chlorinatedpolyethylene, supplied by Allied Chemical Corp, New York, N. Y.

These results show that in each case the metal salts of the EXAMPLE VIalkyl maleate half-esters improve the retention of physical propertiesparticularly with regard to ultimate elongation. This property isconsidered the more sensitive criterion of failure on weathering andhigh retention is desirable. Loss of tensile modulus and yield strengthindicates increase in stiffness, and high retention of these propertiesis also desirable.

EXAMPLE IV In samples 3, 7, 8, l2, 14, 15, 19, 20, 25-30, 32, 33, and35-42 of Examples I-III, the poly(vinyl chloride) resin (Geon 103 EPF 7)is replaced with an identical quantity of the resins listed in a. to d.below (or blended with reinforcing modifiers such as listed in e. to j.below) to give plastic compositions having excellent heat and lightstability properties:

a. after-chlorinated poly(vinyl chloride) The following plasticcompositions in the Table below are compounded according to theprocedures of the preceding Examples, using parts of poly(vinylchloride) (Geon 103 EPF 7) in every case.

styl maleate l.0 phr dibutyl tin maleate l.0 phr magnesium monocetylmaleate l.0 phr dibutyl tin bis(mono l.0 phr calcium monolauryl methylmaleate) maleate l.0 phr di-n-octyl tin bis 0.50 phr sodium monocetyl(monomethyl maleate) maleate l.0 phr di-n-octyl tin bis 0.30 phraluminum mono-n- (monomethyl maleate) octyl maleate 1.5 phr dibutyl tinbis(mono 0.75 phr magnesium mono-nstearyl maleatej octyl fumarate l.5phr dibutyl tin maleate 0.75 phr aluminum monocetyl fumarate 1.5 phrdi-n-octyl tin 0.50 phr calcium monolauryl dilaurate fumarate 1.5 phrdi-n-octyl maleate 0.50 phr magnesium mono stearyl itaconate 2.0 hrdibutyl tin dilaurate 0.30 phr sodium monocetyl itaconate 2.0 phrdibutyl tin bis( mono 0.30 phr calcium monolauryl methylmaleate)itaconate 2.0 phr dibutyl tin maleatc 0.75 phr aluminum monomyri stylitaconate 2.0 phr di-n-octyl tin l.0 phr aluminum mono-ndilaurate octylcitraconate 2.5 phr di-n-octyl bis 1.0 phr magnesium mono (monomethylmaleate cetyl citraconate 2.5 phr dibutyl tin maleate 1,0 phr sodiummonostearyl citraconate 2.5 phr di-n-octyl tin dilaurate l.25 phrmagnesium mono stearyl mesaconate 2.5 phr di-n-octyl tin maleate 4- L25phr calcium monocetyl mesaconate 2.5 phr di-n-octyl bis(mono 1.25 phraluminum monomyri methyl maleate) styl mesaconate 3.0 phr dibutyl tinmaleate 0.75 phr sodium monolauryl mesaconate 3.0 phr dibutyl tindilaurate l.5 phr sodium mono-noctyl glutaconate 3.0 phr di-n-octyl tinmaleate l.0 phr calcium monocetyl glutaconate 3.0 phr dibutyl tin bis(mono 0.30 phr magnesium mono methyl maleate) stearyl glutaconate 3.0 phrdibutyl tin maleate 0.30 phr aluminum mono lauryl glutaconate The aboveplastic compositions are found to possess excellent heat and lightstability characteristics.

Milled sheets of the above formulations were exposed to a Xenon arc aspreviously described.

Sample No. Results 46 Moderate discoloration after l700 hours 47 Slightdiscoloration after 1700 hours No discoloration after 2000 hours Theabove results show the further improvement in light stability obtainedwhen an organotin mercaptoester is used in conjunction with an organotincarboxylate and a metal salt of the monoalkyl esters of theherein-described unsaturated dicarboxylic acids.

Similar results are obtained when the dibutyl tin B-mercaptopropionateis replaced with:

di-n-octyl tin B-mercaptopropionate dibutyl tin bis(2-ethylhexylthioglycollate) di-n-octyl tin bis( Z-ethylhexyl thioglycollate) dibutyltin bis(laurylmercaptide) dibutyl tin bis(hexadecylmercaptide) I claim:

1. A plastic composition comprising:

a. a chlorine-containing polymer selected from the group consisting of ahomopolymer of vinyl chloride, a copolymer of vinyl chloride with otherethylenically unsaturated monomers and mixtures of said homopolymer orcopolymer of vinyl chloride with polymers derived from otherethylenically unsaturated monomers;

. an dialkyltin salt of an acid selected from the group consisting of asaturated aliphatic monocarboxylic acid containing up to 12 carbon atomsin the carboxylate moiety, maleic acid, and half-esters of maleic acidderived from a saturated aliphatic alcohol having up to 18 carbon atomsor cyclohexanol; and

c. a metal salt of a monoalkyl ester of an unsaturated dicarboxylicacid; wherein the metal cation of said salt is sodium, calcium,magnesium, or aluminum; the monoalkyl radical contains from eight to 18carbon atoms; and said unsaturated dicarboxylic acid is selected fromthe group consisting of maleic acid, fumaric acid, itaconic acid,citraconic acid, mesaconic acid, and glutaconic acid, wherein theproportion by weight of said organotin salt per hundred parts ofchlorine-containing polymer is from 0.5 to 3.0, and the proportion byweight of said metal salt per hundred parts of chlorine-containingpolymer is from 0.30 to 1.50.

2. A plastic composition comprising: a. a chlorine-containing polymerselected from the group b. an organotin carboxylate selected from thegroup consisting of dibutyl tin dilaurate, dibutyl tin maleate,di-n-octyl tin dilaurate, di-n-octyl tin maleate, dibutyl tin bis(monocyclohexyl maleate), di-n-octyl tin bis(monocyclohexyl maleate),di-butyl tin bis(monomethyl maleate), and din-octyl tin bis(monomethylmaleate), and dibutyl tin bis(mono-2-ehtylhexyl maleate); and

c. a metal salt selected from the group consisting of magnesiummonostearyl maleate, aluminum monostearyl maleate, calcium monostearylmaleate, sodium monostearyl maleate, magnesium monostearyl fumarate,aluminum monostearyl fumarate, calcium monostearyl fumarate, and sodiummonostearyl fumarate.

3. A plastic composition comprising: a. a chlorine-containing polymerselected from the group consisting of a homopolymer of vinyl chloride, acopolymer of vinyl chloride with other ethylenically unsaturatedmonomers and mixtures of said homopolymer or copolymer or vinyl chloridewith polymers derived from other ethylenically unsaturated monomers;

b. an dialkyltin salt of an acid selected from the group consisting of asaturated aliphatic monocarboxylic acid con taining up to 12 carbonatoms in the carboxylate moiety, maleic acid, and half-esters of maleicacid derived from a saturated aliphatic alcohol having up to 18 carbonatoms or cyclohexanol;

c. a metal salt of a monoalkyl ester of an unsaturated dicarboxylicacid; wherein the metal cation of said salt is sodium, calcium,magnesium, or aluminum; the monoalkyl radical contains from eight to 18carbon atoms; and said unsaturated dicarboxylic acid is selected fromthe group consisting of maleic acid, fumaric acid, itaconic acid,citraconic acid, mesaconic acid, and glutaconic acid, and the proportionby weight of said organotin salt per hundred parts ofchlorine-containing polymer is from 0.5 to 3.0, and the proportion byweight of said metal salt per hundred parts of chlorine-containingpolymer is from 0.30 to 1.50; and

d. an organotin mercaptoester or an organotin mercaptide.

4. A lubricating heat and light stabilizer composition forchlorine-containing polymers which comprises:

a. a dialkyltin salt of an acid selected from the group consisting of asaturated aliphatic monocarboxylic acid containing up to 12 carbon atomsin the carboxylate moiety, maleic acid and half-esters of maleic acidderived from a saturated aliphatic alcohol having up to 18 carbon atomsor cyclohexanol.

. a metal salt of a monoalkyl ester of an unsaturated dicarboxylic acid;wherein the metal cation of said salt is sodium, calcium, magnesium, oraluminum; the monoalkly radical contains from eight to 18 carbon atoms;and said.

unsaturated dicarboxylic acid is selected from the group consisting ofmaleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconicacid, and glutaconic acid; wherein the ratio by weight of said organotinsalt to said metal'saltis from 0.33 to 10.

5. A lubricating heat and light stabilizer composition forchlorine-containing polymers which comprises:

11 2f UNTTED STATES PATENT @FFTCE QERTTTTQATE @F CRRECTTN Patent 3",6 4h246 Dated Februarv 22., 1972 l lerr-ill Lozanov It is certified thaterror appears in the above-identified patent and that said LettersPatent/are hereby corrected as shown below:

Please correct the inventor's name (twice occurred) "Lozanou" to LozanovPlease correct the corporate name of assignee "Chas. Pfizer &: 00.,Inc," to Pfizer Inc:

Signed and sealed this 3rd day of October 1972.

(SEAL) Attest:

EDWARD DTQFLETCHER ,JRQ ROBERT GOTTSCHALK Commissioner of PatentsAttesting (Dfjicer UNITE STATES PATENT OFFICE QREHFECAE @F CUREC'HQDated E b IiL lXiL -9u Patent No. 3..,.e m.aue

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

Please correct the inventor's name (twice occurred) "Lozanou" t0 LozanovPlease correct the corporate name of assignee "Chas. Pfizer 8c C0,,Inc," to Pfizer Inc,

Signed and sealed this 3rd day of October 1972.

(SEAL) Attest:

EDWARD MBFLETCHER ,JRG ROBERT GOTTSCHALK Commissioner of PatentsAttesting; Officer

2. A plastic composition comprising: a. a chlorine-containing polymerselected from the group consisting of poly(vinyl chloride), afterchlorinated poly(vinyl chloride), a vinyl chloride-vinyl acetatecopolymer, a vinyl chloride-propylene copolymer, a vinyl ether-vinylchloride copolymer, a mixture of poly(vinyl chloride) with chlorinatedpolyethylene, and a miXture of a vinyl ester-ethylene modifiedpoly(vinyl chloride); b. an organotin carboxylate selected from thegroup consisting of dibutyl tin dilaurate, dibutyl tin maleate,di-n-octyl tin dilaurate, di-n-octyl tin maleate, dibutyl tinbis(monocyclohexyl maleate), di-n-octyl tin bis(monocyclohexyl maleate),di-butyl tin bis(monomethyl maleate), and di-n-octyl tin bis(monomethylmaleate), and dibutyl tin bis(mono-2-ehtylhexyl maleate); and c. a metalsalt selected from the group consisting of magnesium monostearylmaleate, aluminum monostearyl maleate, calcium monostearyl maleate,sodium monostearyl maleate, magnesium monostearyl fumarate, aluminummonostearyl fumarate, calcium monostearyl fumarate, and sodiummonostearyl fumarate.
 3. A plastic composition comprising: a. achlorine-containing polymer selected from the group consisting of ahomopolymer of vinyl chloride, a copolymer of vinyl chloride with otherethylenically unsaturated monomers and mixtures of said homopolymer orcopolymer or vinyl chloride with polymers derived from otherethylenically unsaturated monomers; b. an dialkyltin salt of an acidselected from the group consisting of a saturated aliphaticmonocarboxylic acid containing up to 12 carbon atoms in the carboxylatemoiety, maleic acid, and half-esters of maleic acid derived from asaturated aliphatic alcohol having up to 18 carbon atoms orcyclohexanol; c. a metal salt of a monoalkyl ester of an unsaturateddicarboxylic acid; wherein the metal cation of said salt is sodium,calcium, magnesium, or aluminum; the monoalkyl radical contains fromeight to 18 carbon atoms; and said unsaturated dicarboxylic acid isselected from the group consisting of maleic acid, fumaric acid,itaconic acid, citraconic acid, mesaconic acid, and glutaconic acid, andthe proportion by weight of said organotin salt per hundred parts ofchlorine-containing polymer is from 0.5 to 3.0, and the proportion byweight of said metal salt per hundred parts of chlorine-containingpolymer is from 0.30 to 1.50; and d. an organotin mercaptoester or anorganotin mercaptide.
 4. A lubricating heat and light stabilizercomposition for chlorine-containing polymers which comprises: a. adialkyltin salt of an acid selected from the group consisting of asaturated aliphatic monocarboxylic acid containing up to 12 carbon atomsin the carboxylate moiety, maleic acid and half-esters of maleic acidderived from a saturated aliphatic alcohol having up to 18 carbon atomsor cyclohexanol. b. a metal salt of a monoalkyl ester of an unsaturateddicarboxylic acid; wherein the metal cation of said salt is sodium,calcium, magnesium, or aluminum; the monoalkly radical contains fromeight to 18 carbon atoms; and said unsaturated dicarboxylic acid isselected from the group consisting of maleic acid, fumaric acid,itaconic acid, citraconic acid, mesaconic acid, and glutaconic acid;wherein the ratio by weight of said organotin salt to said metal salt isfrom 0.33 to
 10. 5. A lubricating heat and light stabilizer compositionfor chlorine-containing polymers which comprises: a. an organotincarboxylate selected from the group consisting of dibutyl tin dilaurate,dibutyl tin maleate, di-n-octyl tin dilaurate, di-n-octyl tin maleate,dibutyl tin bis (monocyclohexyl maleate), di-n-octyl tinbis(monocyclohexyl maleate), di-butyl tin bis (monomethyl maleate),di-n-octyl tin bis(monomethyl maleate), and dibutyl tinbis(mono-2-ethylhexyl maleate); and b. a metal salt selected from thegroup consisting of magnesium monostearyl maleate, aluminum monostearylmaleate, calcium monostearyl maleate, sodium monostearyl maleate,magnesium monostearyl fumarate, aluminum monostearyl fumarate, calciummonostearyl fumarate, and sodium monostearyl fumarate.